CN103619859A - 磷光材料的制备及其应用 - Google Patents
磷光材料的制备及其应用 Download PDFInfo
- Publication number
- CN103619859A CN103619859A CN201280026446.0A CN201280026446A CN103619859A CN 103619859 A CN103619859 A CN 103619859A CN 201280026446 A CN201280026446 A CN 201280026446A CN 103619859 A CN103619859 A CN 103619859A
- Authority
- CN
- China
- Prior art keywords
- platinum
- title complex
- hydrogen
- alkyl
- heterocycle carbine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 title description 15
- 239000003446 ligand Substances 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000005401 electroluminescence Methods 0.000 claims abstract 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- -1 aminocarboxyl Chemical group 0.000 claims description 27
- 125000001118 alkylidene group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 11
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- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
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- 239000005864 Sulphur Substances 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 125000004423 acyloxy group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 7
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
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- 239000011669 selenium Substances 0.000 claims description 7
- 125000005504 styryl group Chemical group 0.000 claims description 7
- 125000003107 substituted aryl group Chemical group 0.000 claims description 7
- 125000004149 thio group Chemical group *S* 0.000 claims description 7
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
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- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
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- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 4
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- QKOQVAHXBZOYME-UHFFFAOYSA-M sodium N,N-dimethylformamide dodecyl sulfate Chemical compound [Na+].CN(C)C=O.CCCCCCCCCCCCOS([O-])(=O)=O QKOQVAHXBZOYME-UHFFFAOYSA-M 0.000 description 3
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- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明主要涉及用于铂(II)配合物制备的双-(N-杂环卡宾)亚烷基四齿配体的铂(II)配合物、四齿双-(N-杂环卡宾)亚烷基配体以及它的配位体前体。铂(II)配合物的量子效率被提高了,具有深蓝色的蓝光发射,可以用于带有双-(N-杂环卡宾)亚烷基配体的铂(II)配合物的电致发光层的OLED制模。
Description
相关申请
该申请要求享有美国临时申请的优先权,在先申请的申请号为61/491,711,申请日为2011年5月31日。因此也包括表格、图例、制图在内的全文内容的参考文献。
技术领域
本发明涉及一类磷光材料、该类材料的制备方法以及使用此类材料的有机发光二极管(OLED)。
背景技术
最初的有机发光二极管是由唐等人在(U.S.Patent4,356,429)和在(Appl.Phys.Lett.1987,51,12,913)中首次披露的。随后出现大量关于OLED器件结构及其发光材料应用的研究。这些发光二极管对元件有如下要求:(1)超薄;(2)自发光;(3)低工作电压且高效能;(4)高对比度和高分辨率的显示。
OLED元件具备的25%的单峰和75%的三线态激子,因此磷光材料成为放射性材料发展的主要方向。磷光材料制备元件的显示效率一般要高于荧光材料制备元件。铂配合物是一类能够提供高发光量子效率和良好热稳定性的放射性材料。高性能的OLEDs采用铂(Ⅱ)配合物制备(Yan et al.,Appl.Phys.Lett.2007,91(6)063508;Che et al.,Chemistry-A EuropeanJournal2010,16(1),233)。
尽管制备蓝色发光磷光材料已被证明具有挑战性,仍然无法通过铂(Ⅱ)配合物制备高性能和使用寿命长的蓝色发光OLEDs。要调整铂(Ⅱ)配合物的发光颜色,适当的共轭长度的配位体是必不可少的。制备蓝色发光的中性铂(II)配合物,通过协调两个二齿配位体到Pt(II)中心,从而得到最初的蓝色发光铂(II)配合物(Brooks et al.,Inorg.Chem.2002,41,3055;and Unger et al.,Angew.Chem.Int.Ed.2010,49,10214)。形成这些双齿配位体铂(II)配合物的元件的寿命和稳定性较四齿铂(II)配合物元件要差。配位体含两个以上的芳基,非共轭单元耦合,没有波长小于480nm的发射峰(U.S.Patent No.7,026,480,U.S.Patent No.6,653,654)。蓝色发光材料不是由此类三齿或四齿配体产生。对于四齿铂(II)蓝色发光材料,共轭基连接配体芳基的研究,未能得到波长小于480nm的发射峰(U.S.Patent No.7,361,415,U.S.Patent No.7,691,495and U.S.Published Patent Application2007/0103060A1)。
N-杂环卡宾(NHC)是强的σ电子供体,但是是弱的π电子受体。Meyer等人在(Organometallics,2011,30(11),2980)中披露,使用环金属铂(II)配合物与π-结合的短配体进行反应,没有发射光谱的报告。
发明内容
本发明的实施例针对包含双-(N-杂环卡宾)亚烷基的四齿配位体,结构见双-阴离子-双-卡宾形式的结构式I:
其中R1-R8分别为氢,氟,氯,溴,碘,羟基,烷基,取代的烷基,环烷基,取代的环烷基,芳基,取代芳基,酰基,烷氧基,酰氧基,氨基,硝基,酰氨基,芳烷基,氰基,羧基,硫代基,苯乙烯基,氨基羰基,氨基甲酰基,芳氧基羰基,苯氧基羰基或烷氧羰基;并且R1-R8中至少有一个不是氢;X是氧,氮-R9,硫,磷-R9,硒,R9为氢或者烷基。本发明一个实施例中,R6不是氢。本发明一个实施例中,R8不是氢。本发明的实施例针对由包含双-(N-杂环卡宾)的配位体制备稳定的蓝色发光铂(Ⅱ)配合物,双-(N-杂环卡宾)的配位体中四齿配体I的电子供体的取代基X在结构Ⅱ铂配合物的阴离子上。
其中R1-R7分别为氢,氟,氯,溴,碘,羟基,烷基,取代的烷基,环烷基,取代的环烷基,芳基,取代芳基,酰基,烷氧基,酰氧基,氨基,硝基,酰氨基,芳烷基,氰基,羧基,硫代基,苯乙烯基,氨基羰基,氨基甲酰基,芳氧基羰基,苯氧基羰基或烷氧羰基;并且R1-R8中至少有一个不是氢;X是氧,氮-R9,硫,磷-R9,硒,R9为氢或者烷基。本发明一个实施例中,R6不是氢。本发明一个实施例中,R8不是氢。
在本发明的一个实施例中,四齿配位体前体的质子化形式:
其中R1-R7分别为氢,氟,氯,溴,碘,羟基,烷基,取代的烷基,环烷基,取代的环烷基,芳基,取代芳基,酰基,烷氧基,酰氧基,氨基,硝基,酰氨基,芳烷基,氰基,羧基,硫代基,苯乙烯基,氨基羰基,氨基甲酰基,芳氧基羰基,苯氧基羰基或烷氧羰基;并且R1-R8中至少有一个不是氢;X是氧,氮-R9,硫,磷-R9,硒,R9为氢或者烷基;A-是氯化物,溴化物,碘化物,甲苯磺酸酯,对溴苯磺酸盐,三氟甲磺酸酯,或其它亲核性低的阴离子。本发明一个实施例中,R6不是氢。本发明一个实施例中,R8不是氢。
制备四齿配位体前体III的一系列反应见图1,其中A-是Br-。合成反应通过X保护的邻卤代反应,咪唑不取代和4-取代,或者4,5-取代苯酚,硫醇,硒醇,苯胺,N-烷基苯胺,磷酸一苯酯或P-烷基磷酸一苯酯。技术纯熟的条件下,可得到N-芳基取代咪唑二取代宝石二卤代烷烃,或功能相当的亲核取代。受保护的前体中XH中的H由保护基团取代,也可以氢取代,例如甲基取代。其反应结果为在X保护的双-(N-杂环卡宾)亚烷基前体中,当出现脱保护时,双-(N-杂环卡宾)亚烷基配位体被提供作为在四质子化形式的前体。根据本发明的一个实施例,典型的四-质子化双-(N-杂环卡宾)亚烷基配位体前体见图2。
根据本发明的一个实施例,典型的四齿双-(N-杂环卡宾)亚烷基配位体铂(II)配合物见图4。根据本发明的一个实施例,四齿双-(N-杂环卡宾)亚烷基配位体铂(II)配合物具有一个电声结构吸收带,最大峰值在350nm左右,摩尔吸光系数约为1×104M-1cm-1,在溶液中,具有结构性弱的发射峰,最大在460nm左右,光量子产率φ超过5%,存在期τ大于1.5μs。根据本发明的一个实施例,双-(N-杂环卡宾)亚烷基配位体铂(II)配合物的蓝光发射,在稀释溶液中具有最大峰值低于470nm以及光量子产率超过5%的蓝光发射。双-(N-杂环卡宾)亚烷基配位体铂(II)配合物是一个平面四边形的中性铂(II)配合物,刚性、热稳定,热分解出现在280℃以上。
在本发明的一个实施例中,质子化的四亚烷基双-(N-杂环卡宾)配位体前体结合Pt(II)盐形成四齿双-(N-杂环卡宾)亚烷基配体的铂(II)配合物,见图3。铂(II)盐可以是溶剂化的或未溶剂化的铂卤化物或者其等效物。例如采用二甲亚砜溶剂化的PtCl2,Pt(DMSO)2Cl2都可以被使用。质子受体,如胺存在下,溶液中发生络合反应。在本发明的一个实施例中,质子受体是一类叔胺,例如但不仅限于以下:三甲胺,三乙胺,吡啶,N,N,N,N-四甲基乙二胺以及1,4-二甲基哌嗪。
根据本发明的一个实施例,四齿双-(N-杂环卡宾)亚烷基配体铂(II)配合物分散并固定化在惰性聚合物基体上,例如但不仅限于以下:聚(甲基丙烯酸甲酯)(PMMA),从而在一个聚合物的重量比大于等于1%的蓝色光谱区域,以形成一个高电子发射膜。室温下通过积分球法测得该膜的绝对量子发射产率为30%左右。溶液中的双-(N-杂环卡宾)亚烷基配体铂(II)配合物在该膜的最大发射峰可出现大小达到10nm的蓝移,从而可以看出聚合物分散体中的固溶体的状态。根据国际照明委员会标准,该膜的发射色度为CIEx,y<0.2和CIEx+y<0.3。如,配合物4,CIEx,y为(0.15,0.10),见图4,接近于较理想的深蓝色,深蓝色的CIEx,y为(0.14,0.10)。
所有的专利和出版物无论在参考文献、全文,还是图或者表格提及或引用本文,均不符合本规范的明确了的实效性。
附图说明
图1所示为四齿双-(N-杂环卡宾)配位体前体的制备反应方案。
图2所示为三个典型的四齿双-(N-杂环卡宾)配位体前体的结构。
图3所示由四齿双-(N-杂环卡宾)配位体前体转换到四齿双-(N-杂环卡宾)配位体配合物的反应方案。
图4为三个典型的四齿双-(N-杂环卡宾)配体的铂(II)配合物4-6的结构。
图5为配合物5的X-射线晶体结构:a)热椭球在50%的概率水平的透视图,为便于观察排除氢原子和溶剂化分子干扰;b)沿c轴的堆积图。
图6为配合物4在二甲基甲酰胺的二氯甲烷溶液(19:1,v/v),十二烷基硫酸钠-二甲基甲酰胺溶液(19:1,v/v)(蓝移),含配合物4的聚(甲基丙烯酸甲酯)膜(1wt%)(仅有发射和进一步蓝移)中的吸收和发射光谱,吸收低于382,发射高于382。
图7为配合物5在二甲基甲酰胺的二氯甲烷溶液(19:1,v/v),十二烷基硫酸钠-二甲基甲酰胺溶液(19:1,v/v)(蓝移),含配合物5的聚(甲基丙烯酸甲酯)膜(1wt%)(仅有发射和进一步蓝移)中的吸收和发射光谱,吸收低于382,发射高于382。
图8为配合物6在十二烷基硫酸钠-二甲基甲酰胺溶液(19:1,v/v)(蓝移),含配合物6的聚(甲基丙烯酸甲酯)膜(1wt%)(仅有发射和进一步蓝移)中的吸收和发射光谱,吸收低于382,发射高于382。
图9为配合物4-7的热重曲线。
图10为构建配合物5所需的带有发光层的典型的OLED所使用的NPB,2-TNATA,TPBi的化学结构。
图11为构建配合物5所需的带有发光层的典型的OLED电致发光光谱。
图12为典型的带有包含配合物5的发光层的OLED的JVB曲线。
具体实施方式
以下通过举例,说明用于实施本发明的程序。但本发明不局限于这些实施例。除非另有说明,百分数均按重量计,所有溶剂混合物的比例按体积计。
发明概要
本发明的实施例针对结构Ⅱ双阴离子四齿双-(N-杂环卡宾)配位体的蓝色磷光铂(II)配合物:其中R1-R8分别为氢,氟,氯,溴,碘,羟基,烷基,取代的烷基,环烷基,取代的环烷基,芳基,取代芳基,酰基,烷氧基,酰氧基,氨基,硝基,酰氨基,芳烷基,氰基,羧基,硫代基,苯乙烯基,氨基羰基,氨基甲酰基,芳氧基羰基,苯氧基羰基或烷氧羰基;X分别为氧,氮,硫,磷,或硒。本发明的其他实施例针对双-(N-杂环卡宾)的四齿配体的制备,其中R1-R8中的至少一个不为氢,并且OLEDs包含四齿双-(N-杂环卡宾)配体的铂(II)配合物。
材料与方法
所有的起始原料为市售材料。光物理测量使用的溶剂为色谱纯级别。由北京中国科学院化学研究所进行元素分析。快原子轰击(FAB)质谱,采用Finnigan Mat95型质谱仪测得。1H(300MHz or400MHz)核磁共振波谱采用DPX300型和Avance400Bruker FT型核磁共振波谱仪进行记录。紫外-可见光谱采用Perkin-Elmer Lambda19型紫外分光光度计测定。298K上的稳态激发和发射光谱以及石英沉积膜上的光致发光通过带有Hamamatsu R928PMT型检测器的Spex1681Flurolog-2Model F111型分光光度计进行测定。除非另行规定,光物理测量所需溶液都在高真空条件下进行至少四次冷冻-抽气-解冻循环进行在线脱气。发射寿命通过Quanta-Ray Q-switch DCR-3Nd:YAG型脉冲激光系统进行测定。发射量子产率采用脱气的乙腈溶液([Ru(bpy)3](PF6)2(bpy=2,2'-bipyridine))进行测定,计算方法为φs=φr(Br/Bs)(ns/nr)2(Ds/Dr),公式中,下标s和r分别指代样品和参比标准溶液,n指代溶剂的折射率,D为积分强度,φ为发光量子产率。B量通过公式B=1–10–AL进行计算,公式中A为激发波长下的吸光度,L为光程长度。波长及φ的误差分别在1nm和10%。
根据文献方法(Lygo等人,Tetrahedron Lett.,1999,40,1389),在K2CO3中通过4-甲基-2-溴苯酚和4-(叔丁基)-2-溴苯酚与MeI的反应,制备4-甲基-2-溴苯甲醚和4-(叔丁基)-2-溴苯甲醚。其中4-甲基-2-溴苯甲醚:84%1H-NMR(400MHz,CDCl3)δ(ppm)7.36(d,J=2.1Hz,1H),7.05(dd,J=8.3Hz,2.1Hz,1H),6.79(d,J=8.3Hz,1H),3.86(s,3H),2.28(s,3H);4-(叔丁基)-2-溴苯甲醚:1H-NMR(300MHz,CDCl3)δ(ppm)7.54(d,J=2.2Hz,1H),7.27(dd,J=8.6Hz,2.2Hz,1H),6.83(d,J=8.6Hz,1H),3.87(s,3H),1.28(s,9H)。
2-(1H-咪唑-1-yl)苯甲醚:在氮气保护下,向含有咪唑(1.0g,15mmol)的脱气的二甲基亚砜溶液(20mL)中添加溴苯甲醚(1.25mL,10mmol),KOH(1.12g,20mmol)和Cu2O(280mg,2mmol)。将得到的混合物在氮气保护下,在140℃搅拌24小时。后冷却至室温,将混合物倒入乙酸乙酯中(EA)(50mL),并过滤。将滤液进行水洗(50mL×3),后用无水硫酸镁干燥。经过旋转蒸发后,粗的油状物采用硅胶柱色谱法进行纯化,洗脱剂采用乙酸乙酯/甲醇(9/1,v/v),得到浅黄色液体(50%)。1H-NMR(400MHz,CDCl3)δ(ppm)7.79(s,1H),7.36(t,J=7.8Hz,1H),7.28(d,J=7.8Hz,1H),7.21(s,1H),7.17(s,1H),7.05(m,2H),3.85(s,3H)。
4-氟-2-(1H-咪唑-1-yl)苯甲醚:在氮气保护下,向含有咪唑(1.0g,15mmol)的脱气的二甲基亚砜溶液(20mL)中添加4-氟-2-溴苯甲醚(1.25mL,10mmol),KOH(1.12g,20mmol)和Cu2O(280mg,2mmol)。将得到的混合物在氮气保护下,在140℃搅拌24小时。后冷却至室温,将混合物倒入乙酸乙酯中(EA)(50mL),并过滤。将滤液进行水洗(50mL×3),后用无水硫酸镁干燥。经过旋转蒸发后,粗的油状物采用硅胶柱色谱法进行纯化,洗脱剂采用乙酸乙酯/甲醇(9/1,v/v),得到浅黄色液体(47%)。1H-NMR(400MHz,CDCl3)δ(ppm)7.82(s,1H),7.21(m,1H),7.17(m,1H),7.07(m,2H),7.00(m,1H),3.84(s,3H)。
4-甲基-2-(1H-咪唑-1-yl)苯甲醚:在氮气保护下,向含有咪唑(1.0g,15mmol)的脱气的二甲基亚砜溶液(20mL)中添加4-甲基-2-溴苯甲醚(1.25mL,10mmol),KOH(1.12g,20mmol)和Cu2O(280mg,2mmol)。将得到的混合物在氮气保护下,在140℃搅拌24小时。后冷却至室温,将混合物倒入乙酸乙酯中(EA)(50mL),并过滤。将滤液进行水洗(50mL×3),后用无水硫酸镁干燥。经过旋转蒸发后,粗的油状物采用硅胶柱色谱法进行纯化,洗脱剂采用乙酸乙酯/甲醇(9/1,v/v),得到浅黄色液体(57%)。1H-NMR(300MHz,CDCl3)δ(ppm)7.78(s,1H),7.16(m,3H),7.09(d,J=1.8Hz,1H),6.94(d,J=8.4Hz,1H),3.81(s,3H),2.33(s,3H)。
4-叔丁基-2-(1H-咪唑-1-yl)苯甲醚:在氮气保护下,向含有咪唑(1.0g,15mmol)的脱气的二甲基亚砜溶液(20mL)中添加4-甲基-2-溴苯甲醚(1.25mL,10mmol),KOH(1.12g,20mmol)和Cu2O(280mg,2mmol)。将得到的混合物在氮气保护下,在140℃搅拌24小时。后冷却至室温,将混合物倒入乙酸乙酯中(EA)(50mL),并过滤。将滤液进行水洗(50mL×3),后用无水硫酸镁干燥。经过旋转蒸发后,粗的油状物采用硅胶柱色谱法进行纯化,洗脱剂采用乙酸乙酯/甲醇(9/1,v/v),得到浅黄色液体(47%)。1H-NMR(400MHz,CDCl3)δ(ppm)7.77(s,1H),7.37(dd,J1=8.6Hz,J2=2.4Hz,1H),7.27(d,J=2.4Hz,1H),7.21(1H),7.17(1H),6.99(d,J=8.6Hz,1H),3.82(s,3H),1.32(s,9H)。
1,1'-双[(2-甲氧基苯基)-1H-咪唑]-3,3'-甲烷二溴化物:在110℃下,含2-(1H-咪唑-1-yl)苯甲醚(0.82g,4.7mmol)和溴甲烷(1mL,14mmol的)溶液在5mL四氢呋喃中回流48h。冷却至室温后通过抽滤得到的白色沉淀物,用四氢呋喃洗涤,经风干得到0.9g固体(73%)。1H-NMR(400MHz,DMSO-d6)δ(ppm)10.01(s,2H),8.30(m,2H),8.22(m,2H),7.64(m,4H),7.41(d,J=8.3Hz,2H),7.22(t,J=7.7Hz,2H),6.90(s,2H),3.90(s,6H)。
1,1'-双[(4-氟-2-甲氧基苯基-1H-咪唑]-3,3'-甲烷二溴化物:在110℃下,含4-氟-2-(1H-咪唑-1-yl)苯甲醚(0.90g,4.7mmol)和溴甲烷(1mL,14mmol)的溶液在5mL四氢呋喃中回流48h。冷却至室温后通过抽滤得到的白色沉淀物,用四氢呋喃洗涤,经风干得到白色固体,产率70%。1H-NMR(400MHz,MeOD)δ(ppm)8.33(d,J=2.1Hz,2H),8.11(d,J=2.1Hz,2H),7.66(m,2H),7.40(m,4H),7.11(s,2H),3.98(s,6H)。注:在MeOD溶剂中,没有出现咪唑NCHN信号。
1,1'-双[(4-甲基-2-甲氧基苯基)-1H-咪唑]-3,3'-甲烷二溴化物:在110℃下,含4-甲基-2-(1H-咪唑-1-yl)苯甲醚(0.88g,4.7mmol)和溴甲烷(1mL,14mmol)的溶液在5mL四氢呋喃中回流48h。冷却至室温后通过抽滤得到的白色沉淀物,用四氢呋喃洗涤,经风干得到白色固体,产率70%。1H-NMR(300MHz,DMSO-d6)δ(ppm)9.93(s,2H),8.26(m,2H),8.20(m,2H),7.47(d,J=1.6Hz,2H),7.44(dd,J1=8.6Hz,J2=1.6Hz,2H),7.31(d,J=8.6Hz,2H),6.86(s,2H),3.88(s,3H),2.33(s,3H)。
1,1'-双[(4-叔丁基-2-甲氧基苯基)-1H-咪唑]-3,3'-甲烷二溴化物:在110℃下,含4-叔丁基-2-(1H-咪唑-1-yl)苯甲醚(1.08g,4.7mmol)和溴甲烷(1mL,14mmol)的溶液在5mL四氢呋喃中回流48h。冷却至室温后通过抽滤得到的白色沉淀物,用四氢呋喃洗涤,经风干得到白色固体,产率74%。1H-NMR(400MHz,DMSO-d6)δ(ppm)10.00(s,2H),8.31(m,2H),8.24(m,2H),7.64(m,4H),7.33(d,J=8.8Hz,2H),6.89(s,2H),3.89(s,3H),1.28(s,18H)。
1,1'-双[(2-羟基苯基)-1H-咪唑鎓]-3,3'-甲烷二溴化物:在120℃下,1,1'-双[(2-甲氧基苯基)-1H-咪唑]-3,3'-甲烷二溴化物(0.81g,1.55mmol)溶液在溴化氢(48wt.%aq.6.5mL)/醋酸(6.5mL)混合溶液中加热回流48h。反应结束后,混合物经旋转蒸发,得到残余物加入丙酮,生成褐色固体沉淀,经乙酸乙酯洗涤并过滤,使用二甲基甲酰胺/乙酸乙酯使之再沉淀,得到白色固体(0.52g,68%)。1H-NMR(400MHz,DMSO-d6)δ(ppm)11.08(br s,2H),9.99(s,2H),8.29(s,2H),8.22(s,2H),7.57(d,J=7.86Hz,2H),7.44(t,J=7.77Hz,2H),7.19(d,J=8.13Hz,2H),7.06(t,J=7.58Hz,2H),6.90(s,2H)。
1,1'-双[(4-氟-2-羟基苯基)-1H-咪唑鎓]-3,3'-甲烷二溴化物(1):在120℃下,1,1'-双[(4-氟-2-甲氧基苯基)-1H-咪唑鎓]-3,3'-甲烷二溴化物溶液在溴化氢(48wt.%aq.6.5mL)/醋酸(6.5mL)混合溶液中加热回流48h。反应结束后,混合物经旋转蒸发得到残余物,加入丙酮,棕色固体析出,经乙酸乙酯洗涤并过滤,使用甲醇/乙酸乙酯使之再沉淀,得到白色固体,产率84%。1H-NMR(300MHz,MeOD)δ(ppm)9.97(im NCHN,s,active),8.23(d,J=2.0Hz,2H),8.13(d,J=2.0Hz,2H),7.52(dd,J1=8.4Hz,J2=3.0Hz,2H),7.26(td,J1=9.0Hz,J2=3.0Hz,2H),7.14(dd,J1=9.0Hz,J2=4.8Hz,2H),7.00(s,2H)。
1,1'-双[(4-甲基-2-羟基苯基)-1H-咪唑]-3,3'-甲烷二溴化物(2):在120℃下,1,1'-双[(4-甲基-2-甲氧基苯基)-1H-咪唑]-3,3'-甲烷二溴化物溶液在溴化氢(48wt.%aq.6.5mL)/醋酸(6.5mL)混合溶液中加热回流48h。反应结束后,混合物经旋转蒸发,得到残余物加入丙酮,棕色固体析出,经乙酸乙酯洗涤并过滤,使用甲醇/乙酸乙酯使之再沉淀,得到白色固体,产率65%。1H-NMR(300MHz,DMSO-d6)δ(ppm)10.82(br s,2H),9.96(s,2H),8.28(m,2H),8.20(m,2H),7.39(d,J=1.6Hz,2H),7.25(dd,J1=8.4Hz,J2=1.6Hz,2H),7.08(d,J=8.4Hz,2H),6.88(s,2H),2.28(s,6H)。(300MHz,MeOD)δ(ppm)9.91(im NCHN,s,2H),8.20(m,2H),8.09(m,2H),7.43(d,J=1.6Hz,2H),7.28(dd,J1=8.4Hz,J2=1.6Hz,2H),7.03(d,J=8.4Hz,2H),6.98(s,2H),2.35(s,6H)。
1,1'-双[(4-叔丁基-2-羟基苯基)-1H-咪唑鎓]-3,3'-甲烷二溴化物(3):在120℃下,1,1'-双[(4-叔丁基-2-甲氧基苯基)-1H-咪唑]-3,3'-甲烷二溴化物溶液在溴化氢(48wt.%aq.6.5mL)/醋酸(6.5mL)混合溶液中加热回流48h。反应结束后,混合物经旋转蒸发,得到残余物加入丙酮,棕色固体析出,经乙酸乙酯洗涤并过滤,使用二甲基甲酰胺/乙酸乙酯使之再沉淀,得到白色固体,产率62%。1H-NMR(400MHz,DMSO)δ(ppm)10.85(s,2H),9.91(s,2H),8.24(m,4H),7.48(m,4H),7.11(d,J=8.4Hz),6.84(s,2H),1.29(s,18H)。
双[3,3'-(2-苯氧基)-1H-咪唑-2,2'-diylidene的]甲烷-1,1'-二基-铂(II)(7):1,1'-双[(2-羟基苯基)-1H-咪唑鎓]-3,3'-甲烷二溴化物(193mg,0.39mmol),二氯双二甲基亚砜合铂(Pt(DMSO)2Cl2,164mg,0.39mmol)和三乙胺(Et3N,0.325mL,6eq.)的混合物,在80℃下加热6h。反应完成后,冷却至室温,离心,收集物用乙醇、醚冲洗,真空干燥,得到淡黄色固体(60%)。1H-NMR(400MHz,DMSO-d6)δ(ppm)8.34(d,J=2.3Hz,2H),7.71(d,J=2.3Hz,2H),7.69(d,J=8.35Hz,2H),7.06(t,J=7.65Hz,2H),6.92(d,J=8.27Hz,2H),6.57(t,J=7.57Hz,2H),6.31(s,2H)FAB-MS:526.0[M+H]+。C19H14N4O2Pt·H2O平均值:C,41.99;H,2.97;N,10.31。其中:C,42.06;H,2.88;N,9.99。
双[3,3'-[(4-氟-2-苯氧基)-1H-咪唑-2,2'-diylidene的甲烷-1,1'-二基-铂(II)(4):1(207mg,0.39mmol)、二氯双二甲基亚砜合铂(Pt(DMSO)2Cl2,164mg,0.39mmol)、三乙胺(Et3N,0.325mL,6eq.)和乙醇(20mL)的混合物,在80℃下加热6h。反应完成后,冷却至室温,离心,收集物用乙醇、醚冲洗,真空干燥,得到白色固体,产率49%。1H-NMR(400MHz,DMSO-d6)δ(ppm)8.34(d,J=1.8Hz,2H),7.72(d,J=1.8Hz,2H),7.66(d,J=10.5Hz,2H),6.90(m,4H),6.32(s,2H)FAB-MS:561.0[M+H]+。C19H12N4O2Pt·H2O平均值:C,39.38;H,2.44;N,9.67。其中:C,38.77;H,2.40;N,9.35。
双[3,3'-(4-甲基-2-苯氧基)-1H-咪唑鎓-2,2'-diylidene]甲烷-1,1'-二基-铂(II)(5):2(204mg,0.39mmol)、二氯双二甲基亚砜合铂(Pt(DMSO)2Cl2,164mg,0.39mmol)、三乙胺(Et3N,0.325mL,6eq.)和乙醇(20mL)的混合物,在80℃下加热6h。反应完成后,冷却至室温,离心,收集物用乙醇、醚冲洗,真空干燥,得到白色固体,产率56%。1H-NMR(300MHz,DMSO-d6)δ(ppm)8.31(d,J=2.1Hz,2H),7.69(d,J=2.1Hz,2H),7.51(s,2H),6.87(d,J=8.2Hz,2H),6.80(d,J=8.2Hz,2H),6.29(s,2H),2.25(s,6H)FAB-MS:553.0[M+H]+。C21H18N4O2Pt·CH2Cl2平均值:C,41.39;H,3.16;N,8.78。其中:C,41.38;H,3.22;N,8.82。
适用于X-射线衍射分析的5的单晶,由二氯甲烷稀释溶液在空气中缓慢蒸发后得到。正交晶系空间群的络合物结晶见下表1。在图5a中可以看到,配合物5具有沿Pt1-C11轴的C11轴的C2对称。围绕铂(II)的四个键角范围为90±2°,表明了平面四边形的配位构型,其中含铂(II)离子的四齿配体的作用力可以忽略不计。铂-碳(N-杂环卡宾)距离小于 ,这要小于四(N-杂环卡宾)铂(II)()和双(N-杂环卡宾)铂(II)乙炔化物( )。这说明,铂-碳(N-杂环卡宾)具有较强的氢键作用。铂-氧(酚)的距离为,略大于稀土水杨醛合铂(II)(Salphen-Pt(II))()和二氧化氮合铂(II)配合物(N2O2)-Pt(II)()。这可能是由于N-杂环卡宾基团的强烈的反效应引起的弱铂-氧(酚)键合作用。由于两个N-杂环卡宾基团之间具有非共轭C11亚甲基的连接,5的分子具有弯曲的骨架。这些骨架弯曲的分子以头尾共面形式堆叠成无限队列,分子间π-π键距离沿轴 ,见图5b。一个配合物分子的两个酚氧原子上氢键键合一个溶剂化的水分子,无序溶解的二氯甲烷分子置于由5的分子堆叠所形成的列之间的通道中。
表1,配合物3晶体数据
aR=Σ||Fo|–|Fc||/Σ|Fo|.b Rw=[Σw(|Fo|–|Fc|)2/Σw|Fo|2]1/2.
双[3,3'-(4-叔丁基-2-苯氧基)-1H-咪唑-2,2'-diylidene的]甲烷-1,1'-二基-铂(II)(6):含3(237mg,0.39mmol),二氯双二甲基亚砜合铂(Pt(DMSO)2Cl2,164mg,0.39mmol)和三乙胺(0.325mL,6eq.)的混合物在20mL乙醇中加热至80℃,加热6h。反应完成后,混合物冷却至室温,离心收集物真空环境下用乙醇、醚冲洗,得到白色固体,产率58%。1H-NMR(400MHz,DMSO-d6)δ(ppm)8.42(d,2.3Hz,2H),7.71(d,2.3Hz,2H),7.52(d,J=2.3Hz,2H),7.08(dd,J1=8.6Hz,J2=2.3Hz,2H),6.83(d,J=8.6Hz,2H),6.30(s,2H),1.29(s,18H)FAB-MS:638.2[M+H]+。平均值:C27H30N4O2Pt·H2O:C,49.46;H,4.92;N,8.55。其中:C,49.36;H,4.64;N,8.46。
配合物4-7的吸收和发射光谱见下表2,溶液测定采用四氢呋喃-二甲基甲酰胺(19:1,v/v)。所有配合物都显示了最大峰值在350nm左右的电子振动吸收光谱,摩尔消光系数约为1×104M-1cm-1。在溶液中,配合物5和6显示出弱结构性的发射峰,中心位置在约460nm附近,量子产率8%,周期1.8μs,明显由于未取代配体的配合物7。带有配位氧苯酚的吸电子取代基的配合物4的蓝移的最大发射波长在443nm处,具有18%的高量子产率,以及3.5μs的长周期。选用二氯甲烷-二甲基甲酰胺(19:1,V/V)代替四氢呋喃-二甲基甲酰胺作为溶剂,观察到配合物4-7的发射峰的5nm的红移。配合物4-6的代表性的吸收和发射光谱示见图6-8。
在惰性聚合物(在实施例中为聚(甲基丙烯酸甲酯)(PMMA))中的配体分散液制备的膜上测定,配合物4-7在蓝色光谱区域具有很强的发射,配合物与聚合物的质量比低至1%。在室温条件下,配合物4-7采用四氢呋喃-二甲基甲酰胺,最大发射峰具有10nm的蓝移动,固态膜的绝对发射量子产率通过积分球法测量,在实验误差内测得约30%,以此可以看出膜上的固-溶状态。所有的膜都具有发射,色度为CIEx,y<0.2(CIEx,y=Commission Internationalede L’Eclairage coordinates(国际照明委员会坐标))和CIEx+y<0.3,值得注意的是配合物4的膜CIEx,y为(0.15,0.10),接近了理想的深蓝色(CIEx,y为(0.14,0.10))。
表2,配合物4-7的光物理参数
[a]采用溶液浓度2×10-5M的四氢呋喃-二甲基甲酰胺溶液(19:1,v/v),记录各项数值为:吸收峰的肩峰出现在305nm,发射峰最大波长350nm。采用1%的聚甲基丙烯酸甲酯膜,记录数值为:发射峰最大波长350nm。
配合物4-6在氮气环境下的热分解温度分别为410℃,390℃,400℃,其热重分析见图9。配合物4-6满足OLED制模的这些配合物的热解沉积条件,同时配合物4-6的热分解起始温度要大于配合物7的250℃的热分解起始温度。
在蓝色OLED中配合物6被用作磷光掺杂剂。器件结构为ITO/2-TNATA(40nm)/NPB(20nm)/DP4-Pt3%(30nm)/TPBi(40nm)/LiF(0.5nm)/Al(100nm)。2-TNATA,NPB和TPBi分别作为空穴注入层(HIL),空穴输送层(HTL)以及电子传输层(ETL)。DP4主机由北京阿格蕾雅科技发展有限公司提供。基于专利性的考虑,化学结构不便透露。所有的材料,在不破坏真空度的情况下,进行连续的高真空热沉积。待整个沉积过程完成后,设备加玻璃盖封装,并在室温条件下进行测试。电致发光采PR650光谱仪进行记录,电源采用K2400设备。
采用配合物6进行OLED的制模,配合物6经真空沉积后作为OLED发光层的掺杂剂,该OLED的配置如下:ITO/2-TNATA(40nm)/NPB(20nm)/DP4-Complex102(30nm)/TPBi(40nm)/LiF(0.5nm)/Al(100nm)。2-TNATA,NPB和TPBi,分别作为空穴注入层,空穴输送层以及电子传输层,其结构见图10。采用宽缝主机(DP4,北京阿格蕾雅科技发展有限公司提供)的配合物6的共沉积,其掺杂水平为3wt%。元件的电致发光光谱和JVB曲线分别见图11,12。电压为15V出现1200cd/m2的最大亮度。该元件在电压为11V的色度为CIEx,y(0.16,0.16),进入到了蓝色光谱区域。电压为11V时,峰的发光效率为0.5cd/A。
需要明确的是文中所描述的例子和实施例仅出于说明目的,其后的任何的修改或变动的信息,本技术领域的技术人员都会知晓,同时其变动及修改内容也将被包括在本申请及权利要求书的范围之内。此外,本文所公开的任何发明或实施例的任何元素或限制条件可以与本文其他任何发明或实施例的任何和/或所有元素或限制条件(单独地或以任何组合形式)组合使用,同时,所有这样的组合都属于本发明的范围,但不仅限于此。
Claims (22)
2.根据权利要求1所述的四齿配位体,其中R6或R8由吸电子取代基所取代。
3.根据权利要求1所述的四齿配位体,其中R6为氟。
4.根据权利要求1,四齿配体A的前体结构如下:
其中,R1-R8分别为氢,氟,氯,溴,碘,羟基,烷基,取代的烷基,环烷基,取代的环烷基,芳基,取代芳基,酰基,烷氧基,酰氧基,氨基,硝基,酰氨基,芳烷基,氰基,羧基,硫代基,苯乙烯基,氨基羰基,氨基甲酰基,芳氧基羰基,苯氧基羰基或烷氧羰基,
其中,R1-R8中的至少一个不为氢,
其中,X分别为氧,氮-R9,硫,磷-R9,或硒,其中R9是氢或烷基,
其中,A-是氯化物,溴化物,碘化物,甲苯磺酸酯,对溴苯磺酸盐,三氟甲磺酸酯,或其它亲核性低的阴离子。
5.根据权利要求4所述的前体,其中R6或R8是由吸电子取代基所取代的。
6.根据权利要求4所述的前体,其中R6为氟。
7.根据权利要求4所述的前体,其中A-是溴化离子。
8.根据权利要求4所述的前体,其结构如下:
10.根据权利要求4所述的前体,其中XH中的H被甲基或其他保护基所取代。
12.根据权利要求11,四齿双-(N-杂环卡宾)亚烷基配体的铂(II)配合物,其中R6,或R8是由吸电子取代基所取代的。
13.根据权利要求11,四齿双-(N-杂环卡宾)亚烷基配体的铂(II)配合物,其中R6为氟。
14.根据权利要求11,四齿双-(N-杂环卡宾)亚烷基配体的铂(II)配合物,其中四齿配体的铂(II)配合物具有最大波长小于470纳米的蓝光发射。
15.根据权利要求14四齿双-(N-杂环卡宾)亚烷基配体的铂(II)配合物,其中,四齿配体的铂(II)配合物具有在溶液中量子效率至少5%的蓝光发射。
17.根据权利要求11,四齿双-(N-杂环卡宾)亚烷基配体的铂(Ⅱ)配合物的制备方法,根据权利要求4所述的前体在质子受体的存在下与Pt(II)盐结合。
18.根据权利要求17所述方法,其中,质子受体为叔胺。
19.根据权利要求17所述方法,其中,铂(II)盐为Pt(II)卤化物。
20.根据权利要求17所述方法,其中,铂(II)卤化物是二氯双二甲基亚砜合铂(Pt(DMSO)2Cl2)。
21.有机发光二极管(OLED),其特征在于具有权利要求11所述的带有四齿双-(N-杂环卡宾)亚烷基配体的铂(II)配合物的电致发光层。
22.根据权利要求21所述的有机发光二极管(OLED),其中四齿双-(N-杂环卡宾)亚烷基配体的铂(II)配合物在稀释溶液中具有弱结构性的蓝光发射,最大波长小于470nm,量子产率φ大于5%。
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